Chemical Modification of Kola-Nut (Cola Nitida) Testa for Adsorption of Cu2+, Fe2+, Mg2+, Pb2, and Zn2+ from Aqueous Solution," Makara Journal of Science: Vol

Makara Journal of Science

Volume 24 Issue 1 March Article 5

1-24-2020

Chemical Modification of ola-NutK (Cola Nitida) Testa for Adsorption of Cu2+, Fe2+, Mg2+, Pb2, and Zn2+ from Aqueous Solution

Nwafor Ogechi Slyvanus Department of Pure and Industrial Chemistry, University of Port Harcourt, Port Harcourt 500272, Nigeria

Chukwu Uche John Department of Pure and Industrial Chemistry, University of Port Harcourt, Port Harcourt 500272, Nigeria, [email protected]

Horsfall Mike Jnr Department of Pure and Industrial Chemistry, University of Port Harcourt, Port Harcourt 500272, Nigeria

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Recommended Citation Slyvanus, Nwafor Ogechi; John, Chukwu Uche; and Jnr, Horsfall Mike (2020) "Chemical Modification of Kola-Nut (Cola Nitida) Testa for Adsorption of Cu2+, Fe2+, Mg2+, Pb2, and Zn2+ from Aqueous Solution," Makara Journal of Science: Vol. 24 : Iss. 1 , Article 5. DOI: 10.7454/mss.v24i1.11727 Available at: https://scholarhub.ui.ac.id/science/vol24/iss1/5

This Article is brought to you for free and open access by the Universitas Indonesia at UI Scholars Hub. It has been accepted for inclusion in Makara Journal of Science by an authorized editor of UI Scholars Hub. Chemical Modification of ola-NutK (Cola Nitida) Testa for Adsorption of Cu2+, Fe2+, Mg2+, Pb2, and Zn2+ from Aqueous Solution

Cover Page Footnote The authors are grateful to the Department of Pure and Industrial Chemistry, University of Port Harcourt for making their research laboratory accessible.

This article is available in Makara Journal of Science: https://scholarhub.ui.ac.id/science/vol24/iss1/5 Makara Journal of Science, 24/1 (2020), 3139 doi: 10.7454/mss.v24i1.11727

Chemical Modification of Kola-Nut (Cola Nitida) Testa for Adsorption of Cu2+, Fe2+, Mg2+, Pb2, and Zn2+ from Aqueous Solution

Nwafor Ogechi Slyvanus, Chukwu Uche John*, and Horsfall Mike Jnr.

Department of Pure and Industrial Chemistry, University of Port Harcourt, Port Harcourt 500272, Nigeria

*E-mail: [email protected]

Received February 26, 2019 | Accepted January 27, 2020

Abstract

In this study, kola-nut testa samples were modified with 0.1 M acetic acid and 0.1 M EDTA at room temperature. The modified Kola-nut testa samples were then characterized with respect to their pH at point of zero charge, melting point, specific gravity, Fourier-transform infrared (FTIR) spectra, and solubility. The characterization results of the modified Kola-nut testa (MKT) revealed that it was sparingly soluble in water, ethanol, and acetone but insoluble in n-hexane. The MKT had a specific gravity of 0.992 ± 0.020 and exhibited various pH values of 4.50 ± 0.50 and 12.00 ± 0.50 at the point of zero charges. The FTIR spectra of the MKT indicated the presence of –OH and –NH groups at 3310.97 cm−1, alkyl groups at 2928.53 cm−1, and aromatic rings at 1612.27–1529.81 cm−1. The results of the adsorption studies at various time intervals indicated that MKT had the capacity to adsorb Fe2+, Mg2+, Zn2+, Cu2+, and Pb2+ as follows: 1.90 ± 0.30 mg/g, 1.80 ± 0.20 mg/g, 1.40 ± 0.20 mg/g, 0.10 ± 0.01 mg/g, and 0.05 ± 0.01 mg/g, respectively. Thus, Fe2+, Mg2+, and Zn2+ were quantitatively removed from the aqueous solutions, whereas Cu2+ and Pb2+ were not. The adsorption of Fe2+, Mg2+, Zn2+, Cu2+, and Pb2+ by MKT from the aqueous medium was dependent on certain factors such as pH, temperature, adsorbent dosage, contact time, and initial metal-ion concentration.

Keywords: modified kola-nut testa, agro waste, adsorption, heavy-metal ions, EDTA

Introduction material. For example, urban waste facilities in Nanyang, China supply over twenty thousand homes The utilization of agro-waste materials in the with biogas [8]. In other regions of the world, remediation of wastewaters containing heavy metals has specifically the United States, some farmers convert generated a lot of interest from researchers because of their agro-wastes into biogas (methane) to generate all the availability of these materials at no cost and their the fuel they need to run their farms in situ [9]. The biodegradability [1]. Agro-wastes have been found to be entire process is cost-effective and the agro-waste effective in the treatment of effluents laden with heavy generated can be endlessly recycled and reused, thereby metals [2-3]. Agro-waste materials like tur-dal husks, greatly minimizing their environmental burden and tamarind husks, and Bengal gram husks could be used associated health hazards. These applications of agro- as adsorbents for the decontamination of effluents laden wastes greatly reduce the disease burden of pollutants in with Hg2+, Fe3+, Ni2+, and Cr6+.3 Other researchers have the environment. utilized agro-waste materials in the adsorption of heavy metals from aqueous solution [4-7]. The versatility of Anthropogenic sources are largely responsible for the agro-waste in water treatment processes has received contamination of natural water supplies with heavy equal attention [2]. metals [5], and researchers have expressed grave concern about the consequences of heavy metals in the However, the utilization of agro-waste materials for environment [4, 10-16]. Long-term exposure to heavy other purposes may have cost implications because metals is known to be deleterious to human health [17]. some agricultural products generate relatively high The physical properties of heavy metals, i.e., good volumes of agro-waste at the point of processing [1]. electrical conduction, strength, rich hue, durability, and Examples of these produces include sugarcane, kola good optical properties [18], have led to their presence nuts, groundnuts, oranges, mangos, watermelons, in virtually all aspects of contemporary life [19]. To grains, and blood and bones from slaughter houses. The negate their impact on the environment, the need to cost implication, however, is minimal compared to the remove them from wastewaters has gained much gain derived from the end use of the agro-waste attention from both ‘town and gown’ communities

31 March 2020  Vol. 24  No. 1 32 Nwafor, et al.

around the world. The shortcomings of conventional spectrophotometer (Brucker: 12028429). The pH was methods in the removal of heavy metals from aqueous measured using a Hanna pH meter (Model H12211), solution, including their non-biodegradability and high and the pH at point of zero charge was determined ac- cost and energy requirements, necessitates research to cording to the method described in the literature [31- identify low-cost biodegradable materials [20-21]. 32].

The use of rice husks [22], the barks of dead biomass Preparation of metal ion solutions. A concentration of [23], peanut testa [6, 24], onion skins [7, 25], and 100 ppm was prepared for each of the following metal- several other agro-waste materials26 have been reported ion solutions (Pb2+, Zn2+, Cu2+, Fe2+, and Mg2+) by de- in the removal of heavy metals from aqueous solutions. termining the appropriate masses of their salts using a However, there is no documentation of reports on the Radway Analytical Balance (Model AS220/C/2). The use of kola-nut waste in the removal of heavy metals. In following amounts of metal salts were obtained: A Southern Nigeria, the processing of kola nuts generates a 0.1598 g of Pb(NO3)2, 0.3357 g of (CH3COO)2Zn.2H2O, tremendous amount of waste, which is indiscriminately 0.3174 g of CuSO4.5H2O, 0.6448 g of (NH4)2SO4.Fe discarded in the environment and constitutes a nuisance O4.6H2O, and 0.6905 g of MgCl.6H2O. Each of these [27]. Were it to be fully harnessed, this “nuisance” metal salts was dissolved in 1000-ml volumetric flasks could offer a potential solution to water pollution with deionized water. problems. Phytochemical analysis of the kola-nut reveals that it contains tannins, alkaloids, saponins, Adsorption studies. The capacity of MKT to adsorb the glycosides, volatile oils, and steroids [28], which provides heavy-metal ions (Pb2+, Zn2+, Cu2+, Fe2+ and Mg2+) from a scientific basis for its various uses. According to aqueous solution was investigated under different equi- numerous reports, the chemical modification of agro- librium conditions (temperature, pH, contact time, ini- waste can greatly enhance the sorption capacity for tial metal-ion concentration, and adsorbent dose). Five heavy metals in aqueous solutions [6, 7, 23, 25, 29, 30]. (5) ml of each metal-ion stock solution was used to Thus, in this work; we explore the potential of make up 50 ml with deionized water in 250-ml Erlen- unmodified and chemically modified kola-nut testa in meyer flasks. The pH of each metal solution in the the adsorption of some heavy metals. flasks (working solution) was set to 6.0 using appropriate buffer solutions. Methods To each metal solution, we added 0.2010 g of MKT and Sample preparation. In this experiment, we used ana- the mixtures were agitated for 2 h at room temperature. lytical-grade reagents obtained from BDH. Fresh sam- Then, we filtered the mixtures through Whatmann No. ples of kola nuts were obtained from the Omuma com- 13 filter paper and collected the filtrates in sterile plastic munity in the state of Rivers, Nigeria and were properly containers. The final metal-ion concentration in each identified at the University of Port Harcourt herbarium. filtrate was determined using a Buck Atomic Absorp- The kola nuts were hulled and their testas were washed, tion Spectrophotometer (AAS, Model: 210/211 VGP). sun-dried, and sieved to particles 63 μm in size for sub- The capacity of MKT to adsorb each of the heavy met- sequent treatment with acetic acid and EDTA. als from aqueous solution was then evaluated using Equation 1. Modification and characterization of kola-nut testa. The method reported by Abdullahi [31] was adopted The effect of temperature on the adsorption of the heavy with slight modification. We equilibrated 100 g of kola- metals by MKT from aqueous solution was determined nut testa (63-μm particle size) with 0.1 M acetic acid for by varying the temperatures from 40–80 °C. Each metal 24 hours. The mixture was filtered after 24 hours and salt solution (10 ppm) was prepared from its stock solu- washed several times with deionized water. The residue tion, to which 0.2010 g of MKT was added. The mix- was then oven dried at 100 °C for 3 h and further equili- ture was agitated several times and then transferred to a brated with 0.1 M EDTA for 24 hours. Finally, the mix- thermostat water bath pre-set to the respective temperature was filtered, and the residue was sun-dried. The ture (40–80 °C) for 10 min. At 10-min intervals, the dried residue was kept in a clean plastic bag and labeled mixture at that particular temperature was removed as modified kola-nut testa (MKT). The MKT was then from the water bath, agitated, and filtered through the characterized to determine its specific gravity, solubili- Whatmann No. 13 filter paper. The filtrate was collected ty, melting point, pH at point of zero charge, and infra- and the metal-ion concentration determined using the red spectra. Buck AAS. The amount of heavy-metal ions adsorbed by MKT at each temperature was calculated using the The melting point, solubility, and specific gravity were following mass balance equation [34]: determined using methods described in the literature.31, 32 The functional groups of MKT were determined using = × (1) a table-top Alpha Fourier-transform infrared (FTIR) ஼௢ି஼௘ ܳ௘ ቂ ௠ ቃ ܸ Makara J. Sci. March 2020  Vol. 24  No. 1 Chemical Modification of Kola-Nut (Cola Nitida) Testa 33

where Qe is the amount of heavy-metal ions adsorbed, the neutral charges (i.e., zero charge) at which MKT is (mg/g), Co and Ce are respectively the initial and final expected to effectively adsorb metal ions from aqueous equilibrium metal-ion concentrations (ppm), m is the solution [24, 32-33]. The sum of the charges on the sur- mass of MKT (g), and V is the volume of the metal-ion face of MKT are neutral (net charge is zero) at these solution (L). The amount of heavy-metal ions adsorbed initial pH (pHi) values because at these points the ΔpH by MKT was also expressed in terms of the percentage is zero. Similar results have been reported in the litera- removal, %R, which we calculated using Equation 2: ture [24, 32-33].

( ) % = × 100 (2) The complex nature of MKT became more evident in its ஼௢ି஼௙ IR spectrum (Figure 2). The sharp and broad absorption band at 3310.97 cm−1 can be attributed to the –OH and where Coܴ andቂ Cf஼ are௢ theቃ initial and final metal ion con- N-H stretching modes of alcohols and amines [39]. The centrations of the adsorbate in ppm, respectively [35- −1 intense sharp peak at 1612.27 cm is attributable to the 37]. –C=C- bonds of aromatic rings [39]. The C-H stretching mode of the alkyl groups (CH3,C2H5,C3H7, etc.) exhib- We also determined the effect of varying pH (2.0–10.0) −1 ited weak absorption at 2928.53 cm . MKT also exhib- on the adsorption of heavy metals by MKT, following a ited different absorption bands at the finger print region procedure similar to that described above. In addition, −1 2+ 2+ (1600–800 cm ) [39]. The absorption band at 1300– we studied the adsorption of the metal ions (Pb , Cu , −1 1150 cm was probably due to the C-O stretching Zn2+, Mg2+ and Fe2+) by MKT for different contact-time modes of the acids (RCOOH), esters (RCOOR), or an- intervals. To do so, we varied the contact time of the hydrides (RCOOCOR') [39]. A strong out-of-plane adsorbent (MKT) and adsorbate (metal-ion solution) bending vibration arose from the terminal alkenes from 20–100 min (i.e., 20 min, 40 min, 60 min, 80 min, −1 RCH=CH2 between 800–1000 cm and the sharp band and 100 min) at room temperature. Finally, we investi- −1 at 1100.17 cm is due to secondary alcohols, ROH gated the influence of the initial metal-ion concentration [39]. These MKT absorption frequencies differed slight- and adsorbent dose on the adsorption of heavy metals ly from the IR spectrum of unmodified kola-nut testa by MKT at room temperature. The equilibrium adsorp- (UKT), which is shown in Figure 3. tion of the heavy metals by MKT under these conditions was evaluated using Equation 1, as described by other The melting point of MKT was inconclusive because authors [32, 38]. The experiments were performed in there was no change in physical state (i.e., from solid to triplicate to ensure accuracy and their average values are liquid) during the melting-point investigation (the reported here. thermometer scale range was 0–360 °C). The color of the MKT changed in the temperature range of 70–90 °C Results and Discussion during the melting point investigation. In addition, the MKT contained different mixtures of substances that are Characterization of MKT. MKT was found to be spar- rich in carbon, some of which are susceptible to thermal ingly soluble in water, ethanol, and acetone but insolu- degradation and therefore difficult to melt in a mixture. ble in n-hexane. The specific gravity result obtained for The implication of this MKT behavior is that it MKT was 0.992 ± 0.020. These results indicate that contained a complex mixture of materials with different MKT is relatively dense relative to water. The pH val- melting points and other properties (chemical and ues at the point of zero charge were found to be 4.50 ± physical). 0.50 and 12.00 ± 0.50, as shown in Figure 1, which are

Figure 1. pH at Point of Zero Charge for MKT (n = 3)

Makara J. Sci. March 2020  Vol. 24  No. 1 34 Nwafor, et al.

Figure 2. FTIR Spectrum of Modified Kola-nut Testa (MKT)

Figure 3. FTIR Spectrum of Unmodified Kola-nut Testa (UKT)

Adsorption of heavy metals. MKT was found to have These deviations could be accounted for by the capacity to take up metal ions (Pb2+, Cu2+, Zn2+, reconsidering the chemical treatment and studying the Mg2+, and Fe2+) from an aqueous medium. However, the nature of the heavy metals. It could be argued that the amounts of copper and lead adsorbed were relatively chemical treatment was not entirely successful due to poor. The highest adsorption capacity of MKT for each stearic hindrances between the chelate (EDTA) and of the following metals, Fe2+, Mg2+, Zn2+, Cu2+ and high-molecular-weight substances (bulky groups) likely Pb2+, at various contact-time intervals is as follows: 1.90 present in the kola-nut testa. It is likely that only a ± 0.30 mg/g, 1.80 mg/g ± 0.20, 1.40 mg/g ± 0.20, 0.10 ± limited fraction of EDTA was present in the MKT. 0.01 mg/g, and 0.05 ± 0.01 mg/g, respectively, as presented in Table 1. Secondly, the ligand (EDTA is a hexadentate ligand, i.e., it has six lone pairs of electrons that can fill the The pertinent question to ask at this point is: why was vacant orbitals in the metals) might have been MKT ineffective in adsorbing some heavy-metal ions associated with other groups present in the MKT from aqueous solution considering the fact that EDTA is through chemical interaction (hydrogen bonding, ionic a good complexing agent for the heaviest metal ions. or covalent interaction), thereby limiting the ability of

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MKT to effectively adsorb heavy metals from aqueous metals, as presented in Figure 4. An increase in solution. To this end, relative success was recorded for temperature from 40 °C to 80 °C had little or no effect the adsorption of Zn2+, Mg2+, and Fe2+, whereas the on the general percentage removal of the metal ions. adsorption of Cu2+ and Pb2+ was very poor, as shown in Fe2+ recorded the highest percentage removal with an Table 1. The poor adsorption of the metal ions Cu2+ and average of 73.56 ± 0.6%, followed closely by Mg2+ with Pb2+ may be due to the bulky nature (size) of lead and 71.96 ± 1.0% and Zn2+ with 46.20 ± 0.4%. For the metal copper, which may be difficult for MKT to adsorb ions Cu2+ and Pb2+, adsorption by MKT was very low because of the limited number of sites available for the (below 20.00% for Cu2+ and 3.00% for Pb2+). The adsorption of these metals. In summary, the increasing results further revealed that each metal ion has a unique order of adsorption for the metal ions by MKT is as optimum temperature at which its adsorption from follows: Pb2+ < Cu2+ < Zn2+ < Mg2+ < Fe2. aqueous solution by MKT is favorable. The response of each metal-ion solution during interaction with the Adsorption studies in different equilibration conditions. adsorbent (MKT) varied greatly, which is probably The results obtained regarding the adsorption of the because the aqueous solution was a single-metal ion metal ions (Pb2+, Cu2+, Zn2+, Mg2+, and Fe2+) under solution in which competition with other metal ions was different equilibrium conditions indicated that minimal. temperature influenced the adsorption of these heavy

Table 1. Adsorption Capacities for Some Heavy-metal Ions by MKT at Room Temperature and Constant pH 6.0

Adsorption capacity (mg/g) Metal ion (M2+) Values for MKT Pb2+ 0.05 ± 0.01 Cu2+ 0.10 ± 0.01 Zn2+ 1.40 ± 0.20 Mg2+ 1.80 ± 0.20 Fe2+ 1.90 ± 0.30

Figure 4. Effect of Temperature on the Percentage of Metal Adsorbed Using MKT at Constant pH 6.0

Figure 5. Effect of pH on the Percentage of Metal Adsorbed Using MKT at Room Temperature

Makara J. Sci. March 2020  Vol. 24  No. 1 36 Nwafor, et al.

Figure 6. Effect of Initial Metal Ion on Percentage of Metal Adsorbed by MKT at Room Temperature and Constant pH of 6.0

Figure 7. Effect of Contact Time on Percentage of Metal Adsorbed by MKT at Room Temperature and Constant pH of 6.0 pH has a profound effect on the extraction of heavy- The order of the percentage removal followed the same metal ions from aqueous solutions [40-41]. Figure 3 trend as above, with Fe2+ > Mg2+ > Zn2+ > Cu2+ and Pb2+. shows the results for the adsorption of the metal ions at different pH values (1.0–10.0). From the figure, we can The percentages of metal adsorbed for different contact see that Fe2+ had the highest percentage removal of times (min) by MKT indicate that most of the Fe2+, 81.80% at pH 8.0, closely followed by Mg2+ with Mg2+ and Zn2+ ions were adsorbed throughout the time 76.70% at pH 6.0, and Zn2+ with 56.90% at pH 8.0. of the study (20 min to 100 min), as presented in Figure Once again, the lead and copper ions were least 7. Mg2+ recorded the highest average percentage of adsorbed throughout the pH range of this study. metal adsorbed (72.58% ± 1.20), followed by Fe2+ with Generally, their adsorption was slightly more favorable an average of 63.82% ± 0.80 and Zn2+ with average of at pH 8.0. The values reported for the metal ions in the 53.50% ± 1.00. As usual, the amounts of copper and basic region suggest that precipitation of the metal ions lead adsorbed by MKT were very low, which indicates as insoluble hydroxides M(OH)2 may have contributed that MKT is not an effective adsorbent for the removal to their extraction from the aqueous solution by other of Pb2+ and Cu2+ ions from an aqueous medium. The mechanisms, such as complexation, co-precipitation, or adsorption capacity results of MKT for the metal ions other routes [40-41]. The optimum pH for each metal presented in Table 1 above confirm this conclusion. ion differed considerably. Finally, Figure 8 presents the percentage of metal Figure 6 shows a graphical representation of the adsorbed at different adsorbent doses (grams) by MKT. percentages of metal adsorbed at different metal ion The dosages of the adsorbent ranged from 0.200 g to concentrations by MKT. Increases in the metal-ion 1.000 g. The percentage removal of magnesium (II) concentrations resulted in a corresponding increase in metal ions was highest, with an average value of the percentages of metal ion adsorbed. Optimum values 73.82% ± 1.50, followed by iron (II) metal ions with of 95.00% and 94.30% were recorded for Fe2+ and 75.16% ± 2.55 and zinc (II) metal ions with 46.99% ± Mg2+, respectively, at 50 ppm by MKT. These results 2.32. As anticipated, the copper (II) and lead (II) metal were closely followed by Zn2+ with 85.2%. ions gave very poor average percentage removal values Interestingly, at the very low concentration of 10 ppm, of 30.34% ± 2.74 and 5.84% ± 2.37, respectively. In all, Cu2+ had an optimum adsorption value of 60.1%, which in this experiment, a small quantity of MKT was needed subsequently dropped to 14.9% with further increases in to adsorb the metal ions Fe2+, Mg2+, and Zn2+ from concentration. The percentage removal of Pb2+ was aqueous solutions, whereas Pb2+ and Cu2+ ions could not abysmal, irrespective of the metal ion concentration. be efficiently removed by the adsorbent MKT.

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Figure 8. Effect of Adsorbent Dose (Grams) on Percentage of Metal Adsorbed by MKT at Room Temperature and Constant pH of 6.0

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